This invention relates to a process for producing substituted phenoxyethylamines, intermediates for synthesis of said amines and a process for producing said intermediates. Substituted phenoxyethylamines are useful as synthetic intermediates for substituted phenoxyethyl-aminopyrimidine derivatives exhibiting high activities as insecticides, acaricides (Japanese Unexamined Patent Publications Nos. 3667/1984 and 67/1987).
In the prior art, as the process for synthesizing substituted phenoxyethylamines, there have been known the processes shown by the following reaction schemes. In the formulae, Ar represents an aryl group.
(1) ArOCH.sub.2 CH.sub.2 Br+NH.sub.3 .fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (2) ArOK+ClCH.sub.2 CH.sub.2 NH.sub.2 .fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (3) ArOCH.sub.2 CONH.sub.2 +LiAlH.sub.4 .fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (4) ArOCH.sub.2 CH.sub.2 Br+potassium phthalimide ##STR3## J. Chem. Soc. 1933, p. 270, U.S. Pat. No. 3,474,134 (5) ArOH+ethyleneimine.fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (6) ArOCH.sub.2 CH.sub.2 NH.sub.2 +hexamethylenetetramine .fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (7) NH.sub.2 CH.sub.2 CH.sub.2 OK+ArX.fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (8) RCH.sub.2 NHOH+R'X.fwdarw.RCH.sub.2 NHOR'.fwdarw.RCH.dbd.NR'.fwdarw.R'NH.sub.2 Chem. Lett., 10, 1057 PA0 (9) ArSO.sub.2 NHCH.sub.2 CH.sub.2 OH+NaOH.fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 (10) ArOCH.sub.2 CN+LiAlH.sub.4 .fwdarw.ArOCH.sub.2 CH.sub.2 NH.sub.2 PA0 2-[4-(2-ethoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[4-(2-ethoxyethyl)-2-methylphenoxy]-acetaldehyde oxime; PA0 2-[4-(2-ethoxyethyl)-2-ethylphenoxy]-acetaldehyde oxime; PA0 2-[2,3-dimethyl-4-(2-ethoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,5-dimethyl-4-(2-ethoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,6-dimethyl-4-(2-ethoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[4-(2-methoxyethyl)-2-methylphenoxy]-acetaldehyde oxime; PA0 2-[2-ethyl-4-(2-methoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,3-dimethyl-4-(2-methoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,5-dimethyl-4-(2-methoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,6-dimethyl-4-(2-methoxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[4-(2-hydroxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[4-(2-hydroxyethyl)-2-methylphenoxy]-acetaldehyde oxime; PA0 2-[2-ethyl-4-(2-hydroxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,3-dimethyl-4-(2-hydroxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,5-dimethyl-4-(2-hydroxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-[2,6-dimethyl-4-(2-hydroxyethyl)phenoxy]-acetaldehyde oxime; PA0 2-phenoxyacetaldehyde oxime, and the like. PA0 2-[4-(2-ethoxyethyl)phenoxy]-ethylamine; PA0 2-[4-(2-ethoxyethyl)-2-methylphenoxy]-ethylamine; PA0 2-[4-(2-ethoxyethyl)-2-ethylphenoxy]-ethylamine; PA0 2-[2,3-dimethyl-4-(2-ethoxyethyl)phenoxy]-ethylamine; PA0 2-[2,5-dimethyl-4-(2-ethoxyethyl)phenoxy]-ethylamine; PA0 2-[2,6-dimethyl-4-(2-ethoxyethyl)phenoxy]-ethylamine; PA0 2-[4-(2-methoxyethyl)phenoxy]-ethylamine; PA0 2-[4-(2-methoxyethyl)-2-methylphenoxy]-ethylamine; PA0 2-[2-ethyl-4-(2-methoxyethyl)phenoxy]-ethylamine; PA0 2-[2,3-dimethyl-4-(2-methoxyethyl)phenoxy]-ethylamine; PA0 2-[2,5-dimethyl-4-(2-methoxyethyl)phenoxy]-ethylamine; PA0 2-[2,6-dimethyl-4-(2-methoxyethyl)phenoxy]-ethylamine; PA0 2-[4-(2-hydroxyethyl)phenoxy]-ethylamine; PA0 2-[4-(2-hydroxyethyl)-2-methylphenoxy]-ethylamine; PA0 2-[2-ethyl-4-(2-hydroxyethyl)phenoxy]-ethylamine; PA0 2-[2,3-dimethyl-4-(2-hydroxyethyl)phenoxy]-ethylamine; PA0 2-[2,5-dimethyl-4-(2-hydroxyethyl)phenoxy]-ethylamine; PA0 2-[2,6-dimethyl-4-(2-hydroxyethyl)phenoxy]-ethylamine; PA0 2-phenoxyethylamine; and the like.
Chem. Ber. 70 (1937) 979 PA1 J. Pharm. Soc. Japan 63 (1943) 546 PA1 Helv. Chemica Acta. 31 (1948) 1397 PA1 J. Amer. Chem. Soc., 73 (1951) 2584 PA1 Roczniki Chem. 661 (1958), C. A. 1961, 2537 PA1 Khim. Prom-St., Ser.; Reakt. Osobo Chist. Ves chestva (2) 1-3 C. A. 92 (3) 22184 q PA1 Tetrahedron Lett., 26. 2289 PA1 J. Amer. Chem. Soc., 109, 4036 (1987)
ArOCH.sub.2 CH.sub.2 Br, which is starting material of the above processes of (1), (4) and (6), can be synthesized only in poor yield because of producing much by-products.
The above processes of (1), (4) and (6) produce much byproducts products during synthesis of ArOCH.sub.2 CH.sub.2 Br, and are poor in yield. The reactions for introducing a substituent into Ar group suffer from many restrictions due to the presence of halogen substituents, and the desired substituted phenoxyethylamines cannot be produced in most cases. The processes of (2) and (5) are extremely poor in yield. The processes of (3) and (10) are not suitable for commercial application because LiAlH.sub.4 is expensive. The process of (7) is dangerous in handling and also expensive, because metallic potassium is used. The process of (8) cannot extend in commercial scale because expensive reagents are used. The process of (9) is defective in that the reaction does not proceed unless the substituent on Ar is p-nitro or the like.
As described above, various problems have been involved in commercial application of the prior art processes. Although the process for producing oxime derivatives from corresponding aldehydes has not been known in the art, the reaction with hydroxylamine-0-alkyl ether is disclosed in Japanese Unexamined Patent Publication No. 260054/1986. When the compounds of the present invention were adapted to be produced by this process, much by-products were formed to give poor yield. Also, when hydroxylamine sulfate, which is advantageous in commercial availability, handling, corrosiveness, etc., was used, there ensued the problem that substantially no reaction proceeded.